<p>Ammonium dinitramide (ADN) is a novel energetic ionic salt, which is an admirable candidate of ammonium perchlorate (AP) for expansive utilized in propellants and explosives. Realizing the rapid heat release and thermal efficiency improvement of ADN is of great significance for its application in the field of propellants and explosives. In this paper, CuO and CuCr₂O₄ nanoparticles (NPs) were prepared by the mechanical ball milling method, and their different properties are compared with the bulk catalysts by various methods. The effects of CuO and CuCr₂O₄ particles on the thermolysis and combustion behavior of ADN were explored by thermogravimetric and differential scanning calorimeter technologies (TG–DSC) and ignition tests. Thermogravimetric-Fourier Transform Infrared-mass spectrometry technologies (TG-FTIR-MS) were employed to determine the evolved gas of ADN and its composites. The results show that CuO and CuCr₂O₄ NPs have high specific surface area with particle size in the range of 20–40&#xa0;nm, and show better catalytic activity than bulk catalysts, which can reduce the exothermic peak temperature of ADN from 192.75 to 151.97&#xa0;°C and 152.36&#xa0;°C, respectively. The ignition experiment proved that copper-based catalysts can significantly accelerate the decomposition of ADN, accompanied by bright flame. TG-FTIR-MS results indicate that thermolysis products of ADN and nano-copper-based catalyst/ADN include NO₂, N₂O, H₂O, and so on. The possible catalytic mechanism is that HN(NO₂)₂ can transfer H⁺ on the surface of CuO/CuCr₂O₄, and form Cu(NO₃)₂, [Cu(NH₃)₂](NO₃)₂ et al., which boosts the early generation of gaseous products. The reason why CuCr₂O₄ NPs possess better thermal catalytic performance for ADN than CuO NPs is analyzed by theoretical calculation. All the results indicate that single nano-copper-based catalysts have great potential for practical application in ADN-based propellants.</p>